Soluble Lignin Recovered from Biorefinery Pretreatment Hydrolyzate Characterized by Lignin–Carbohydrate Complexes

The lignin rendered soluble by lignocellulosic biorefinery pretreatment remains insufficiently understood along the lines of molecular properties and chemical composition. To procure a representative soluble lignin preparation, an aromatic-selective adsorptive resin was utilized. Approximately 90% of soluble lignin could be recovered from autohydrolysis pretreatment hydrolyzate (autohydrolyzate) produced from a hardwood and a nonwood biomass. Adsorbate compositional characterization revealed a befuddling magnitude of carbohydrate in selectively isolated lignin adsorbates. Quantitative structural analysis of the lignin by NMR suggested lignin–carbohydrate complexes (LCCs) as the cause behind the pronounced carbohydrate contents. Analyzed spectra revealed both hardwood and nonwood soluble lignin features of ∼10 total LCC per 100 aromatic rings, with each lignin bearing unique LCC profiles. In addition, native structures remained in large quantities. The improved understanding of hydrolyzate-soluble lignin granted from this work will aid biorefinery development by improving discourse around a biorefinery lignin source.